A structured polymer solar cell architecture featuring a large interface between donor and acceptor with connecting paths to the respective electrodes is explored. To this end, poly-(3-hexylthiophene) (P3HT) nanorods oriented perpendicularly to indium tin oxide (ITO) glass are fabricated using an anodic aluminum oxide template. It is found that the P3HT chains in bulk films or nanorods are oriented differently; perpendicular or parallel to the ITO substrate, respectively. Such chain alignment of the P3HT nanorods enhanced the electrical conductivity up to tenfold compared with planar P3HT films. Furthermore, the donor/acceptor contact area could be maximised using P3HT nanorods as donor and C60 as acceptor. In a photovoltaic device employing this structure, remarkable photoluminescence quenching (88%) and a seven-fold efficiency increase (relative to a device with a planar bilayer) are achieved.